Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2019 May 22;4(5):8731-8738.
doi: 10.1021/acsomega.8b03400. eCollection 2019 May 31.

Temperature-Induced Single-Crystal-to-Single-Crystal Transformations with Consequential Changes in the Magnetic Properties of Fe(III) Complexes

Amit Adhikary  1 , Sohel Akhtar  1 , Anand Pariyar  2 , Andrei S Batsanov  3 , Raju Mondal  1
Affiliations

Temperature-Induced Single-Crystal-to-Single-Crystal Transformations with Consequential Changes in the Magnetic Properties of Fe(III) Complexes

Amit Adhikary et al. ACS Omega. .

Erratum in

Abstract

The present article deals with an one-to-one structure-property correspondence of a dinuclear iron complex, [Dipic(H2O)FeOH]2·H2O (1) (Dipic = pyridine-2,6-dicarboxylic acid). Variable-temperature X-ray single-crystal structural analysis confirms a phase transition of complex 1 to complex 2 ([Dipic(H2O)FeOH]2) at 120 °C. Further, single-crystal-to-single-crystal (SCSC) transformation was monitored by temperature-dependent single crystal X-ray diffraction, powder X-ray diffraction, time-dependent Fourier-transform infrared spectroscopy, and differential scanning calorimetry. SCSC transformation brings the change in space group of single crystal. Complex 1 crystallizes in the C2/c space group, whereas complex 2 crystallizes in the Pi̅ space group. SCSC transformation brings the change in packing diagram as well. Complex 1 shows two-dimensional network through H-bonding, whereas the packing diagram of complex 2 shows a zigzag-like arrangement. Phase transformation not only fetches structural changes but also in the magnetic properties. Difference in Fe-O-Fe bond angles of two complexes creates notable variation in their antiferromagnetic interactions with adjacent metal centers.

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Unit cell of complexes 1 (a) and 2 (b). Color code: Fe, dark yellow; C, gray; N, blue; O, red. (c) Transformation of single crystal of complex 1 to complex 2.
Figure 2
Figure 2
Molecular structure of complex 1 (a) and complex 2 (b). H atoms are omitted for clarity.
Figure 3
Figure 3
(a) Polyhedra of complex 1 and (b) polyhedra of complex 2, illustrating edge sharing between the two polyhedra. Bond distances are shown in Å.
Figure 4
Figure 4
(a) Packing diagram of complex 1 along c-axis, through extensive H-bonding network. (b) Space-fill representation of zigzag arrangement of complex 2 along a-axis. (c) Zigzag packing representation of complex 2 through H-bonding.
Figure 5
Figure 5
H-bonded dimeric unit of (a) complex 1 and (b) complex 2.
Figure 6
Figure 6
π–π interactions of (a) complex 1 and (b) complex 2.
Figure 7
Figure 7
(a, d) Hirshfeld surface of complexes 1 and 2, respectively (dnorm), showing the short contacts at the sites of H-bonding. (b, e) Fingerprints of the O···H intermolecular interactions of complexes 1 and 2, respectively. (c, f) N···H interactions of complexes 1 and 2, respectively, within the crystal packings from the single-crystal X-ray diffraction data in complexes 1 and 2, respectively. The gray zones represent all of the interactions, and the blue zones account for the corresponding O···H and N···H interactions.
Figure 8
Figure 8
Simulated and temperature-dependent experimental X-ray powder diffraction patterns observed from the sample of complex 1.
Figure 9
Figure 9
Comparison of FT-IR spectra of complex 1, complex 1 after heating, and complex 2.
Figure 10
Figure 10
DSC thermogram of complex 1 at the rate of 5 °C/min.
Figure 11
Figure 11
Energy level diagram of complexes 1 and 2, calculated through single-point DFT calculation.
Figure 12
Figure 12
Temperature-dependent dc magnetic susceptibility of complexes 1 and 2. The solid lines indicate fitting of the plots.
Figure 13
Figure 13
Model used for fitting of the χMT vs T plot for complex 1.
Figure 14
Figure 14
Temperature-dependent dc magnetic susceptibility of complexes 1 and 2. The solid lines indicate fitting of the plots considering intermolecular interactions (zJ′).
See this image and copyright information in PMC

References

    1. Duriska M. B.; Neville S. M.; Moubaraki B.; Cashion J. D.; Halder G. J.; Chapman K. W.; Balde C.; Létard J.-F.; Murray K. S.; Kepert C. J.; Batten S. R. A Nanoscale Molecular Switch Triggered by Thermal, Light, and Guest Perturbation. Angew. Chem., Int. Ed. 2009, 48, 2549. 10.1002/anie.200805178. - DOI - PubMed
    1. Liu J-L.; Wu J-Y.; Huang G-Z.; Chen Y. C.; Jia J-H.; Ungur L.; Chibotaru L. F.; Chen X-M.; Tong M-L. Desolvation-Driven 100-Fold Slowdown of Tunneling Relaxation Rate in Co(II)-Dy(III) Single-Molecule Magnets through a Single-Crystal to-Single-Crystal Process. Sci. Rep. 2015, 5, 16621 10.1038/srep16621. - DOI - PMC - PubMed
    1. Chen L.; Ye J-W.; Wang H. P.; Pan M.; Yin S. Y.; Wei Z. W.; Zhang L-Y.; Wu K.; Fan Y-N.; Su C-Y. Ultrafast water sensing and thermal imaging by a metal-organic framework with switchable luminescence. Nat. Commun. 2017, 8, 15985 10.1038/ncomms15985. - DOI - PMC - PubMed
    1. Zhang Y-J.; Liu T.; Kanegawa S.; Sato O. Reversible Single-Crystal-to-Single-Crystal Transformation from Achiral Antiferromagnetic Hexanuclears to a Chiral Ferrimagnetic Double Zigzag Chain. J. Am. Chem. Soc. 2009, 131, 7942. 10.1021/ja901539y. - DOI - PubMed
    1. Ma L.; Yang J.; Lu B. B.; Li C. P.; Ma J. F. Water-Stable Metal–Organic Framework for Effective and Selective Cr2O72– Capture through Single-Crystal to Single Crystal Anion Exchange. Inorg. Chem. 2018, 57, 11746–11752. 10.1021/acs.inorgchem.8b01879. - DOI - PubMed